CN102989490B - Copper-hydroxyapatite catalyst for synthesizing methyl glycolate and ethylene glycol and preparation method thereof - Google Patents
Copper-hydroxyapatite catalyst for synthesizing methyl glycolate and ethylene glycol and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical industry, and particularly relates to an efficient catalyst for synthesizing methyl glycolate and ethylene glycol through gas-phase catalytic hydrogenation of dimethyl oxalate and a preparation method thereof. The catalyst is loaded with copper and other auxiliary metals by taking hydroxyapatite as a carrier. The preparation method of the catalyst comprises the following steps of: firstly preparing a hydroxyapatite suspension from calcium nitrate and diammonium hydrogen phosphate; adding soluble copper salt and soluble auxiliary metal slat, and performing metal loading by an ammonia distillation method; filtering; washing and drying the filter cake; and roasting to obtain a powdery catalyst for the gas-phase catalytic hydrogenation of dimethyl oxalate. Through the invention, controllable selectivity is realized on the hydrogenation products including methyl glycolate and ethylene glycol, the yield of methyl glycolate can reach 80% under low-temperature conditions, and the yield of ethylene glycol can reach 99% under high-temperature conditions; and the preparation method of the catalyst is simple and has good stability and relatively broad prospects in industrial application.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of dimethyl oxalate gas-phase catalytic hydrogenation and prepare copper-based catalysts of methyl glycollate and ethylene glycol and preparation method thereof.
Background technology
Methyl glycollate, has another name called Glycolic acid methyl esters or hydroxy methyl acetate, and molecule, because of simultaneously containing α-H, hydroxyl and ester group, thus has the chemical property of alcohol and ester concurrently.Methyl glycollate is that synthesis has the different tricuspid ester alkali of active anticancer and the important intermediate of analog thereof, is also the raw material of the carrier additives of some raising lubricating oil crushing resistances of synthesis and wearability simultaneously.In addition, the downstream product of a series of high added values can also synthesized by methyl glycollate, such as catalytic hydrogenation can prepare ethylene glycol, hydrolysis can obtain glycolic, carbonylation can obtain malonic acid monomethyl ester, ammonia solution can obtain glycine, oxidative dehydrogenation can obtain glyoxalic acid methylester etc. thus the downstream product branch formed centered by methyl glycollate.
The production technology of current synthesizing methyl glycolate mainly adopts chloroactic acid method or methyl formate coupling method.Above-mentioned production technology often needs a large amount of severe corrosive alkali (caustic soda etc.) or the liquid strong acid (concentrated sulfuric acid, organic sulfonic acid etc.) as catalyst, large to equipment corrosion, simultaneously also to there is production cost high for above-mentioned technique, energy consumption is high, the shortcomings such as productive rate is low, thus cause being difficult to large-scale industrial application, need the methyl glycollate production technology developing a kind of high-efficiency environment friendly badly.
Ethylene glycol, has another name called glycol, is a kind of important Organic Chemicals.Ethylene glycol is widely used in synthesizing polyester terylene, mylar, hygroscopic agent, plasticizer, surfactant etc.Ethylene glycol is the important source material of synthesis PETG (PET), fiber level PET and polyster fibre, by a large amount of for the manufacture of clothing fabric and industrial product; Bottle sheet level PET is widely used in the fields such as packing business, electronic apparatus, health care, building, automobile.In addition, ethylene glycol also can produce alkyd resins, glyoxal etc., also can be used as antifreezing agent.
Industrial production ethylene glycol often adopts epoxyethane method, and it is high that this technique has energy consumption, long flow path, to shortcomings such as glycol selectivity differences; This production technology is large to the degree of dependence of petroleum resources simultaneously, causes product ethylene glycol price large with crude oil price fluctuating range.Therefore, by carrying out synthesizing glycol based on carbon one chemical industry of natural gas or coal-based feedstocks, China is extremely important.
In order to overcome the shortcoming of above-mentioned methyl glycollate and ethylene glycol synthesis technique, from last century the seventies, explore the extensive concern being caused academia and industrial quarters by the production technology of coal-based route and C-1 chemistry synthesizing methyl glycolate and ethylene glycol.This production technology first step is and CO and methyl nitrite gas phase coupling is catalyzed and synthesized dimethyl oxalate, and US P4507494 once reported a kind of Pd-Ti/Al
2o
3catalyst reaches 95% by CO oxalic dimethyl ester is selective; CN 85101616 also once reported a kind of palladium catalyst, and palladium content is 1%, and its life-span long acting height, dimethyl oxalate yield is greater than 95%, and economic benefit is high.At present, by CO synthesizing dimethyl oxalate at China's successful commercialization.Second step is by dimethyl oxalate, and gas phase hydrogenation synthesizing methyl glycolate, the production technology of methyl glycollate continuation hydrogenation synthesizing of ethylene glycol has become study hotspot and the emphasis of current catalytic field.In patent CN 201010148290, reporting a kind of silver-colored silicon oxide catalyst, can 90% reached compared with obtaining the selective of methyl glycollate by Hydrogenation of Dimethyl Oxalate under temperate condition; Report a kind of Cu/HMS catalyst in CN 200810204710 and show higher Hydrogenation of Dimethyl Oxalate activity, can more than 96% be reached to ethylene glycol yield.By Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol, there is environmental protection, the features such as economical and energy saving, but most of catalyst of bibliographical information at present, the selec-tive hydrogenation synthesis to methyl glycollate or ethylene glycol wherein a kind of product can only be realized, how to realize synthesizing two kinds of different products by high efficiency selected while of reacting condition condition on same catalyst, the industrial production for methyl glycollate and ethylene glycol has and important realistic meaning.
Summary of the invention
The object of the invention is to propose a kind of dimethyl oxalate gas-phase catalytic hydrogenation and prepare effective catalyst of methyl glycollate and ethylene glycol and preparation method thereof.
Effective catalyst for dimethyl oxalate gas-phase catalytic hydrogenation synthesizing methyl glycolate and ethylene glycol provided by the invention is a kind of is main active component with copper, doped with other metals a small amount of as auxiliary agent, take hydroxyapatite as the loaded catalyst of carrier.In this catalyst, the mass fraction of active ingredient copper is: 5 ~ 60 %; The mass fraction of promoter metal (in Mg, Ca, Mn, Fe, Co, Ni, Zn, Ag, Au one or more) is 0.2 % ~ 10 %; All the other are carrier hydroxyapatite, and its three's total amount should meet 100%.
Effective catalyst for dimethyl oxalate gas-phase catalytic hydrogenation synthesizing methyl glycolate and ethylene glycol provided by the invention by changing the distribution of reaction temperature selective control hydrogenation products methyl glycollate and ethylene glycol under dimethyl oxalate conversion ratio higher strip part, thus can reach the temperature-controllable selection synthesis of target product.
The concrete preparation process of above-mentioned catalyst is as follows:
(1) by Ca (NO
3)
24H
2o is water-soluble, and regulates pH 7 ~ 12 to make solution I with ammoniacal liquor;
(2) under agitation by (NH
4)
2hPO
4the aqueous solution (0.1 ~ 1 M, control Ca/P=1 ~ 3 (mol/mol)) slowly in instillation solution I, and agitating heating 2-40 h obtains suspension II at 25 ~ 70 DEG C;
(3) a kind of soluble-salt of copper and the soluble-salt of promoter metal are added in above-mentioned suspension II with certain proportion mix, add ammoniacal liquor and regulate pH=7 ~ 12, and obtain suspension III stir 1 ~ 20 h at 25 ~ 70 DEG C after;
(4) stirring reaction after suspension III being continued to be warming up to 80 DEG C, until reaction solution pH=6 ~ 10, stops heating, obtains suspension IV.
(5) above-mentioned suspension IV after filtration, and washing, carries out drying by filter cake, obtain high-efficiency copper based hydroxylapatite catalyst after roasting.
In the present invention, active metal copper species and promoter metal are carried on hydroxyapatite carrier through ammonia still process method simultaneously, because carrier hydroxyapatite has stronger ion-exchange effect, thus active metal copper and promoter metal and carrier have comparatively strong interaction, facilitate the dispersion of copper at catalyst surface, greatly improve the Activity and stabill of catalyst.
Accompanying drawing explanation
Fig. 1 is copper-hydroxyapatite catalyst stability test.
Fig. 2 is copper-hydroxyapatite catalyst XRD collection of illustrative plates.
Detailed description of the invention
The application of the present invention in dimethyl oxalate gas-phase catalytic hydrogenation methyl glycollate and ethylene glycol is further described below by specific embodiment.
Embodiment 1: carrier hydroxyapatite preparation
By 23.52 g Ca (NO
3)
24H
2o is dissolved in 300 mL water, and regulates pH 11 ~ 12 to make calcium nitrate solution (about 0.33 M) with ammoniacal liquor, under agitation 200 mL is contained 7.89g (NH
4)
2hPO
4the aqueous solution (about 0.30 M, Ca/P=1.67 (mol/mol)) slowly instill in above-mentioned calcium nitrate solution, and the suspension that agitating heating 16 h obtains containing carrier apatite at 50 DEG C is stand-by, the mass fraction containing hydroxyapatite in this suspension is about 2 %.
Active metal copper and promoter metal load: by 13.10 g Cu (NO
3)
23H
2o and 3.01 g Fe (NO
3)
39H
2o joins in above-mentioned carrier suspension simultaneously, regulate suspension pH to 11 ~ 12 with ammoniacal liquor, under 30 DEG C of water-baths, raise bath temperature after stirring reaction 14 h, at 80 DEG C, continue stirring reaction, until suspension pH value is 9 ~ 10, stop reaction, obtain the suspension containing catalyst, afterwards it is filtered, spend deionized water 5 times, filter cake is dry through 120 DEG C of bakings, and under Muffle furnace, 10 DEG C/min keeps 5 h after being warming up to 500 DEG C, obtains catalyst powder.
Activity rating: by catalyst powder granulation to 40 ~ 60 order, loads in reactor reaction pipe, with 5% H
2lower 300 DEG C of reduction activation 3 h of/Ar atmosphere.Raw material dimethyl oxalate is dissolved in methyl alcohol (15 wt.%) as reactant liquor, pumps in reaction tube through constant-flux pump, and using pure hydrogen as reaction gas, reaction pressure is 3.0 MPa, and controlling dimethyl oxalate mass space velocity is 0.5 ~ 1.2 h
-1, hydrogen ester ratio is 150 mol/mol.Be 210 DEG C and 250 DEG C with reaction temperature respectively to investigate catalyst activity, after condensation, with gas chromatographic analysis, it forms product.Selec-tive hydrogenation result is shown in table 1.
Embodiment 2: carrier hydroxyapatite preparation
By 23.52 g Ca (NO
3)
24H
2in the water-soluble 300 mL water of O, and regulate pH 11 ~ 12 to make calcium nitrate solution (about 0.33 M) with ammoniacal liquor, under agitation 200 mL are contained 4.39g (NH
4)
2hPO
4the aqueous solution (about 0.20 M, Ca/P=3.0 (mol/mol)) slowly instill in above-mentioned calcium nitrate solution, and the suspension that agitating heating 16 h obtains containing carrier apatite at 50 DEG C is stand-by, the mass fraction containing hydroxyapatite in this suspension is about 2 %.
Active metal copper and promoter metal load: by 13.10 g Cu (NO
3)
23H
2o and 7.56 g Mn (NO
3)
24H
2o is incorporated in the suspension containing carrier hydroxyapatite simultaneously, regulates suspension pH to 10 ~ 11, stirring reaction 6 h under 50 DEG C of water-baths with ammoniacal liquor, raise bath temperature, at 80 DEG C, continue stirring reaction, until suspension pH value is 7 ~ 7.5, stop reaction, obtain the suspension containing catalyst, filter it afterwards, spend deionized water 5 times, filter cake is through 120 DEG C of bakings, keep 5 h at the lower 10 DEG C/min of Muffle furnace is warming up to 500 DEG C, obtain catalyst powder.
Activity rating: by catalyst powder granulation to 40 ~ 60 order, loads in reactor reaction pipe, with 5% H
2the lower 400 DEG C of reduction activation 5h of/Ar atmosphere.Raw material dimethyl oxalate is dissolved in methyl alcohol (10 wt.%) as reactant liquor, pumps in reaction tube through constant-flux pump, and using pure hydrogen as reaction gas, reaction pressure is 3.0 MPa, and controlling dimethyl oxalate mass space velocity is 0.2 ~ 0.8 h
-1, hydrogen ester ratio is 180 mol/mol.Be 220 DEG C and 260 DEG C with reaction temperature respectively to investigate catalyst activity, after condensation, with gas chromatographic analysis, it forms product.Selec-tive hydrogenation result is shown in table 1.
Embodiment 3: carrier hydroxyapatite preparation is with embodiment 1.
Active metal copper and promoter metal load: by 13.10 g Cu (NO
3)
23H
2o and 1.91 g Zn (NO
3)
26H
2o is incorporated in the suspension containing carrier hydroxyapatite simultaneously, regulates suspension pH to 11 ~ 12, stirring reaction 6 h under 50 DEG C of water-baths with ammoniacal liquor, raise bath temperature, at 80 DEG C, continue stirring reaction, until suspension pH value is 7 ~ 7.5, stop reaction, obtain the suspension containing catalyst, filter it afterwards, spend deionized water 5 times, filter cake is through 120 DEG C of bakings, keep 5 h at the lower 10 DEG C/min of Muffle furnace is warming up to 600 DEG C, obtain catalyst powder.
Activity rating is with embodiment 1.
Embodiment 4: carrier hydroxyapatite preparation
By 30.65 g Ca (NO
3)
24H
2in the water-soluble 300 mL water of O, and regulate pH 8 ~ 9 to make calcium nitrate solution (about 0.33 M) with ammoniacal liquor, under agitation 200 mL are contained 7.89g (NH
4)
2hPO
4the aqueous solution (about 0.30 M, Ca/P=2.18 (mol/mol)) slowly instill in above-mentioned calcium nitrate solution, and the suspension that agitating heating 24 h obtains containing carrier apatite at 50 DEG C is stand-by, the mass fraction containing hydroxyapatite in this suspension is about 2 %.
Active metal copper and promoter metal load: by 13.10 g Cu (NO
3)
23H
2o is incorporated in the suspension of above-mentioned carrier hydroxyapatite, regulates suspension pH to 10 ~ 11, stirring reaction 6h under 50 DEG C of water-baths with ammoniacal liquor, raise bath temperature, at 80 DEG C, continue stirring reaction, until suspension pH value is 7 ~ 7.5, stop reaction, obtain the suspension containing catalyst, filter it afterwards, spend deionized water 5 times, filter cake is through 120 DEG C of bakings, keep 5 h at the lower 10 DEG C/min of Muffle furnace is warming up to 600 DEG C, obtain catalyst powder.
Activity rating: by catalyst powder granulation to 40-60 order, loads in reactor reaction pipe, with 5% H
2the lower 400 DEG C of reduction activation 5h of/Ar atmosphere.Raw material dimethyl oxalate is dissolved in methyl alcohol (10 wt.%) as reactant liquor, pumps in reaction tube through constant-flux pump, and using pure hydrogen as reaction gas, reaction pressure is 4.0 MPa, and controlling dimethyl oxalate mass space velocity is 0.5 ~ 1.5 h
-1, hydrogen ester ratio is 200 mol/mol.Be 220 DEG C and 260 DEG C with reaction temperature respectively to investigate catalyst activity, after condensation, with gas chromatographic analysis, it forms product.Selec-tive hydrogenation result is shown in table 1.
Embodiment 5: carrier hydroxyapatite preparation
By 23.52 g Ca (NO
3)
24H
2in the water-soluble 300 mL water of O, and regulate pH 11 ~ 12 to make calcium nitrate solution (about 0.33 M) with ammoniacal liquor, under agitation 200 mL are contained 13.15g (NH
4)
2hPO
4the aqueous solution (about 0.30 M, Ca/P=1.0 (mol/mol)) slowly instill in above-mentioned calcium nitrate solution, and the suspension that agitating heating 4 h obtains containing carrier apatite at 50 DEG C is stand-by, the mass fraction containing hydroxyapatite in this suspension is about 2 %.
Active metal copper and promoter metal load: by 13.10 g Cu (NO
3)
23H
2o and 4.45 g Mg (NO
3)
26H
2o adds in the suspension containing carrier hydroxyapatite simultaneously, regulates suspension pH to 9 ~ 11, stirring reaction 6 h under 50 DEG C of water-baths with ammoniacal liquor, raise bath temperature, at 80 DEG C, continue stirring reaction, until suspension pH value is 7 ~ 7.5, stop reaction, obtain the suspension containing catalyst, filter it afterwards, spend deionized water 5 times, filter cake is through 120 DEG C of bakings, keep 5 h at the lower 10 DEG C/min of Muffle furnace is warming up to 700 DEG C, obtain catalyst powder.
Activity rating is with embodiment 2.
Embodiment 6: carrier hydroxyapatite preparation
By 23.52 g Ca (NO
3)
24H
2in the water-soluble 300 mL water of O, and regulate pH 11 ~ 12 to make calcium nitrate solution (about 0.33 M) with ammoniacal liquor, under agitation 200 mL are contained 7.89g (NH
4)
2hPO
4the aqueous solution (about 0.30 M, Ca/P=1.67 (mol/mol)) slowly instill in above-mentioned calcium nitrate solution, and the suspension that agitating heating 36 h obtains containing carrier apatite at 50 DEG C is stand-by, the mass fraction containing hydroxyapatite in this suspension is about 2 %.
Active metal copper and promoter metal load: by 9.24 g CuCl
22H
2o and 0.87 g AuCl
3hCl4H
2o adds in the suspension containing carrier hydroxyapatite simultaneously, regulates suspension pH to 8 ~ 9, stirring reaction 6 h under 40 DEG C of water-baths with ammoniacal liquor, raise bath temperature, at 100 DEG C, continue stirring reaction, until suspension pH value is 6.5 ~ 7, stop reaction, obtain the suspension containing catalyst, filter it afterwards, spend deionized water 5 times, filter cake is through 100 DEG C of bakings, keep 6 h at the lower 10 DEG C/min of Muffle furnace is warming up to 300 DEG C, obtain catalyst powder.
Activity rating: by catalyst powder granulation to 40-60 order, loads in reactor reaction pipe, with 5% H
2lower 250 DEG C of reduction activation 2 h of/Ar atmosphere.Raw material dimethyl oxalate is dissolved in methyl alcohol (5 wt.%) as reactant liquor, pumps in reaction tube through constant-flux pump, and using pure hydrogen as reaction gas, reaction pressure is 2.0 MPa, and controlling dimethyl oxalate mass space velocity is 1.0 ~ 2.0 h
-1, hydrogen ester ratio is 80 mol/mol.Be 200 DEG C and 240 DEG C with reaction temperature respectively to investigate catalyst activity, after condensation, with gas chromatographic analysis, it forms product.Selec-tive hydrogenation result is shown in table 1.
Embodiment 7: carrier hydroxyapatite preparation is with embodiment 1.
Active metal copper and promoter metal load: by 2.05 g Cu (NO
3)
23H
2o and 1.10 g Zn (NO
3)
26H
2o adds in the suspension containing carrier hydroxyapatite simultaneously, regulates suspension pH to 10 ~ 11, stirring reaction 6 h under 50 DEG C of water-baths with ammoniacal liquor, raise bath temperature, at 80 DEG C, continue stirring reaction, until suspension pH value is 7 ~ 7.5, stop reaction, obtain the suspension containing catalyst, filter it afterwards, spend deionized water 5 times, filter cake is through 120 DEG C of bakings, keep 5 h at the lower 10 DEG C/min of Muffle furnace is warming up to 600 DEG C, obtain catalyst powder.
Activity rating is with embodiment 1.
Embodiment 8: carrier hydroxyapatite preparation is with embodiment 1.
Active metal copper and promoter metal load: by 10.91 g Cu (NO
3)
23H
2o and 1.70 g Zn (NO
3)
26H
2o joins in the suspension containing carrier hydroxyapatite, regulates suspension pH to 10 ~ 11, stirring reaction 6h under 50 DEG C of water-baths with ammoniacal liquor, raise bath temperature, at 80 DEG C, continue stirring reaction, until suspension pH value is 7 ~ 7.5, stop reaction, obtain the suspension containing catalyst, filter it afterwards, spend deionized water 5 times, filter cake is through 120 DEG C of bakings, keep 5 h at the lower 10 DEG C/min of Muffle furnace is warming up to 600 DEG C, obtain catalyst powder.
Activity rating: by catalyst powder granulation to 40-60 order, loads in reactor reaction pipe, with 5% H
2lower 250 DEG C of reduction activation 8 h of/Ar atmosphere.Raw material dimethyl oxalate is dissolved in methyl alcohol (5 wt.%) as reactant liquor, pumps in reaction tube through constant-flux pump, and using pure hydrogen as reaction gas, reaction pressure is 4.0 MPa, and controlling dimethyl oxalate mass space velocity is 1.5 ~ 2.5 h
-1, hydrogen ester ratio is 100 mol/mol.Be 210 DEG C and 250 DEG C with reaction temperature respectively to investigate catalyst activity, after condensation, with gas chromatographic analysis, it forms product.Selec-tive hydrogenation result is shown in table 1.
Embodiment 9: carrier hydroxyapatite preparation
By 23.52 g Ca (NO
3)
24H
2in the water-soluble 300 mL water of O, and regulate pH 11 ~ 12 to make calcium nitrate solution (about 0.33 M) with ammoniacal liquor, under agitation 200 mL are contained 4.39g (NH
4)
2hPO
4the aqueous solution (about 0.20 M, Ca/P=3.0 (mol/mol)) slowly instill in above-mentioned calcium nitrate solution, and the suspension that agitating heating 16 h obtains containing carrier apatite at 50 DEG C is stand-by, the mass fraction containing hydroxyapatite in this suspension is about 2 %.
Active metal copper and promoter metal load: by 21.31 g Cu (NO
3)
23H
2o and 2.25 g Zn (NO
3)
26H
2o and 3.01 g Fe (NO
3)
39H
2o joins in the suspension containing carrier hydroxyapatite simultaneously, regulates suspension pH to 10 ~ 11, stirring reaction 16 h under 50 DEG C of water-baths with ammoniacal liquor, raise bath temperature, at 80 DEG C, continue stirring reaction, until suspension pH value is 6 ~ 7, stop reaction, obtain the suspension containing catalyst, filter it afterwards, spend deionized water 5 times, filter cake is through 120 DEG C of bakings, keep 5 h at the lower 10 DEG C/min of Muffle furnace is warming up to 600 DEG C, obtain catalyst powder.
Activity rating is with embodiment 1.
Embodiment 10: carrier hydroxyapatite preparation
By 23.52 g Ca (NO
3)
24H
2in the water-soluble 300 mL water of O, and regulate pH 11 ~ 12 to make calcium nitrate solution (about 0.33 M) with ammoniacal liquor, under agitation 400 mL are contained 7.89g (NH
4)
2hPO
4the aqueous solution (about 0.10 M, Ca/P=1.67 (mol/mol)) slowly instill in above-mentioned calcium nitrate solution, and the suspension that agitating heating 16 h obtains containing carrier apatite at 50 DEG C is stand-by, the mass fraction containing hydroxyapatite in this suspension is about 1 %.
Active metal copper and promoter metal load: by 33.81 g CuSO
45H
2o and 2.68 g Zn (NO
3)
26H
2o joins in the suspension containing carrier hydroxyapatite simultaneously, regulates suspension pH to 11 ~ 12, stirring reaction 12 h under 50 DEG C of water-baths with ammoniacal liquor, raise bath temperature, at 80 DEG C, continue stirring reaction, until suspension pH value is 7 ~ 7.5, stop reaction, obtain the suspension containing catalyst, filter it afterwards, spend deionized water 5 times, filter cake is through 120 DEG C of bakings, keep 5 h at the lower 10 DEG C/min of Muffle furnace is warming up to 600 DEG C, obtain catalyst powder.
Activity rating is with embodiment 1.
Embodiment 11: carrier hydroxyapatite preparation is with embodiment 1.
Active metal copper and promoter metal load: by 9.44 g Cu (NO
3)
23H
2o and 1.29 g Zn (NO
3)
26H
2o and 0.61 g AgNO
3join in the suspension containing carrier hydroxyapatite simultaneously, regulate suspension pH to 10 ~ 11 with ammoniacal liquor, stirring reaction 6 h under 70 DEG C of water-baths, raise bath temperature, at 100 DEG C, continue stirring reaction, until suspension pH value is 7 ~ 7.5, stop reaction, obtain the suspension containing catalyst, filter it afterwards, spend deionized water 5 times, filter cake is through 120 DEG C of bakings, keep 5 h at the lower 10 DEG C/min of Muffle furnace is warming up to 500 DEG C, obtain catalyst powder.
Activity rating is with embodiment 1.
Embodiment 12: carrier hydroxyapatite preparation is with embodiment 6.
Active metal copper and promoter metal load: by 9.44 g Cu (CH
3cOO)
2h
2o and 1.29 g Zn (NO
3)
26H
2o and 0.59 g AuCl
3hCl4H
2o joins in the turbid liquid hanged containing carrier simultaneously, regulates suspension pH to 9 ~ 10, stirring reaction 6 h under 30 DEG C of water-baths with ammoniacal liquor, raise bath temperature, at 80 DEG C, continue stirring reaction, until suspension pH value is 6.5 ~ 7, stop reaction, obtain the suspension containing catalyst, filter it afterwards, spend deionized water 5 times, filter cake is through 120 DEG C of bakings, keep 3 h at the lower 10 DEG C/min of Muffle furnace is warming up to 300 DEG C, obtain catalyst powder.
Activity rating is with embodiment 6.
Subordinate list 1 each embodiment activity rating data
Catalyst of the present invention can control dimethyl oxalate gas phase selective hydrogenation product by changing reaction temperature efficiently as can be seen from Table 1, wherein can reach 80% to methyl glycollate yield under cryogenic, can reach 99% under hot conditions to ethylene glycol yield.
Above embodiment is only for illustrating technical scheme of the present invention, although be described the technology of the present invention by embodiment is reasonable, but will be understood by those skilled in the art that, corresponding modify or replacement can be carried out to technical scheme of the present invention, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in claim of the present invention.
Claims (6)
1., for a preparation method for the catalyst of dimethyl oxalate gas-phase catalytic hydrogenation synthesizing methyl glycolate and ethylene glycol, it is characterized in that concrete steps are as follows:
(1) by Ca (NO
3)
24H
2o is water-soluble, and regulates pH to be 7 ~ 12 with ammoniacal liquor, makes solution I;
(2) under agitation by (NH
4)
2hPO
4solution slowly instill in solution I, (NH
4)
2hPO
4solution be 0.1 ~ 1 M, control Ca/P=1 ~ 3 (mol/mol); Agitating heating 2-40 h at 25 ~ 70 DEG C, obtains suspension II;
(3) a kind of soluble-salt of copper and the soluble-salt of promoter metal are added in above-mentioned suspension II by ratio of components, mix, add ammoniacal liquor and regulate pH=7 ~ 12, and stir 1 ~ 20 h at 25 ~ 70 DEG C, obtain suspension III;
(4) stirring reaction after suspension III being continued to be warming up to 80 ~ 100 DEG C, until reaction solution pH=6 ~ 10, stops heating, obtains suspension IV;
(5) above-mentioned suspension IV after filtration, washing, dry, then after roasting, namely obtain high-efficiency copper based hydroxylapatite catalyst;
Wherein, promoter metal is one or more in Mg, Ca, Mn, Fe, Co, Ni, Zn, Ag, Au.
2. preparation method as claimed in claim 1, it is characterized in that, the soluble-salt of described copper is the one of copper nitrate, Schweinfurt green, copper sulphate, copper chloride.
3. preparation method as claimed in claim 2, it is characterized in that, the soluble-salt of described promoter metal is nitrate, chloride or acetate.
4. preparation method as claimed in claim 3, is characterized in that, in step (5), sintering temperature is 300 ~ 700 DEG C, and roasting time is 2 ~ 20h.
5. preparation method as claimed in claim 4, is characterized in that, must carry out activation process before using through following steps:
The catalyst of preparation is carried out granulation, filters out 40-60 object catalyst granules and put into fixed bed reactors; At H
2under/Ar mixed atmosphere, 200 ~ 500 DEG C process 2 ~ 8 hours, carry out activating and reducing; Using pure hydrogen as reaction raw materials after reduction terminates, controlling reaction pressure is 1 ~ 4 MPa, fixed bed reactors bed temperature 100 ~ 300 DEG C, pumps in fixed bed reactors by constant-flux pump by dimethyl oxalate methanol solution, and controlling dimethyl oxalate mass space velocity is 0.1 ~ 2.5 h
-1, hydrogen ester ratio is 80 ~ 200 mol/mol.
6. the catalyst for dimethyl oxalate gas-phase catalytic hydrogenation synthesizing methyl glycolate and ethylene glycol obtained by the described preparation method of one of claim 1-5, it is characterized in that, using hydroxyapatite as carrier, it is main active component that load has with copper, using one or more in Mg, Ca, Mn, Fe, Co, Ni, Zn, Ag, Au as promoter metal component, wherein, the mass fraction of Cu is: 5 ~ 60 %; The mass fraction of promoter metal is 0.2 ~ 10 %; All the other are carrier hydroxyapatite.
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| CN105251521B (en) * | 2015-11-19 | 2017-12-15 | 中科合成油淮南催化剂有限公司 | Loaded transitional metal phosphide catalyst and preparation method and application |
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| CN115999593B (en) * | 2022-11-29 | 2024-05-07 | 中国石油大学(华东) | Catalyst for preparing low-carbon carboxylic acid from low-carbon alcohol and application of catalyst |
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